Self-assembly of porphyrin nanostructures at the interface between two immiscible liquids
Creators
- 1. The Bernal Institute and Department of Chemical Sciences, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland
- 2. School of Chemistry, National University of Ireland, Galway, University Road, Galway, Ireland
- 3. School of Chemistry, and Tyndall National Institute, University College Cork, Cork, T12 YN60 Ireland
- 4. The Bernal Institute and Department of Physics, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland
- 5. CNRS-Université de Lorraine, LCPME UMR 7564, 405 Rue de Vandoeuvre, 54600 Villers-lès-Nancy, France
Description
One of the many evolved functions of photosynthetic organisms is to synthesize light harvesting nanostructures from photoactive molecules such as porphyrins. Engineering synthetic analogues with optimized molecular order necessary for the efficient capture and harvest of light energy remains challenging. Here, we address this challenge by reporting the self-assembly of zinc(II) meso-tetrakis(4-carboxyphenyl)porphyrins into films of highly ordered nanostructures. The self-assembly process takes place selectively at the interface between two immiscible liquids (water|organic solvent), with kinetically stable interfacial nanostructures formed only at pH values close to the pKa of the carboxyphenyl groups. Molecular dynamics simulations suggest that the assembly process is driven by an interplay between the hydrophobicity gradient at the interface and hydrogen bonding in the formed nanostructure. Ex situ XRD analysis and in situ UV/vis and steady state fluorescence indicates the formation of chlathrate type nanostructures that retain the emission properties of their monomeric constituents. The self-assembly method presented here avoids the use of acidic conditions, additives such as surfactants and external stimuli, offering an alternative for the realization of light-harvesting antennas in artificial photosynthesis technologies.
Notes
Files
2020_J_Phys_Chem_C_Manuscript_Open_Access.pdf
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Additional details
Funding
- Designing Reactive Functionalised Soft Interfaces _ Self-healing soft materials for solar energy conversion, energy storage, and sustainable low cost hydrogen production 13/SIRG/2137
- Science Foundation Ireland
- Diffractive optics and photonic probes for efficient mouldable 3D printed battery skin materials for portable electronic devices 14/IA/2581
- Science Foundation Ireland
- LiONSKIN - Moldable Li-ion battery outer skin for electronic devices 13/TIDA/E2761
- Science Foundation Ireland
- Advanced Battery Materials for High Volumetric Energy Density Li-ion Batteries for Remote Off-Grid Power 15/TIDA/2893
- Science Foundation Ireland
- SOFT-PHOTOCONVERSION – Solar Energy Conversion without Solid State Architectures: Pushing the Boundaries of Photoconversion Efficiencies at Self-healing Photosensitiser Functionalised Soft Interfaces 716792
- European Commission